Process for making color couplers



Patented Oct. 11, 1949 UNlTE D-flS T'AT PROCESS FOR MAKING coLoncoUPLnns Arnold Weissberger and Ilinari Salminen,

Rochester, N.- -Y.,'-assignors to Eastman Kodak Company, Rochester I New Jersey N Drawing.

1 This invention relates to particularly to a novel method of preparing couplers for color photography.

Color forming compounds which react with the 2 development product of aromatic amino developing agents to form :coloredimages on photographic developmenthave been the subject of numerous prior-patents. The dyes formed in this way are insoluble in water and in the ordinary photographic developing and fixing baths,

although the silver images formed simultaneously with, them during the photographic development may be removed fromthephotographic layer to leave pure dye imagesin .thelayer. Such a com- 4 pound which isempl'oyed conjunction with the developing agent 'for thesilver and which couples with the development product'of the developer during photographic development is referred to herein as a coupling component or coupler.

When these "couplingcomponents areincorpo rated in the photographic layer prior to exposure, they do notaffect theexposure and development of the layer in the usual way'but when the development is carriedout with a suitable developing agent they combine withthe oxida-;.

tion product of the developer toform a colored image in situ with'the silver image. i

The couplingportion ofthe coupler molecule usually consists of a radicalzwith a phenolichydroxyl group or a'reactivemethylene group,.and

to this portion may be attached;substituents which render the coupler suitable for use in variousprocesses, such asthose described in Mannes and Godowskyfi s; Patent 2,304,940, granted December 15, 1942, Jelleyand Vittum U. S. Pat

ent 2,322,027, grantedJune 15,1943, andQPcterson U. S. Patent 2,296,306, granted September 22, 1942; In the process of thePetersonpatent, for example, couplersare used containing irnino or mercapto groups which permit the formation vention to provide a novel method for the prep- ,9

A further object is td provide a method for the preparation ofcouplers suitable for use in the process of Peterson U. S. 5

aration of color couplers.

Patent 2,296,306. Other objects will appear from the following description of our invention.

These objects are accomplished, according to the broader aspects of our invention bynj ining two different primary or secondary amines,;=orie -5 I or both of which may be, couplers," or one of which may be a heterocycliclcompound containing a reactiveniercapto or imino group, or one of which may be a non coupling aliphatic or aromatic amine, by means of a'two-step condenphotography and activity to saidiamines. j

, N. a corporation of npplication october so, 1943, Serial No. 508,392

6 Claims. (01. 260309 I sation involving theuse of an acyl halide having replaceable halogen atoms of different re- More' specifically, our invention provides for the joining of a coupler containin an amino group, to another amine, such as a heterocyclic compound containing an amino group, by the use of bromoacetyl bromide or sulfobenzoyl dichloride as the condensing agent.

Couplers containing amino groups are well known. Porter and Weissberger U. S. Patent 2,376,380, granted May 22, 1945, describes amino pyrazolones; French Patent 836,144 discloses aminophenols.

If these or similar couplers containing amino groups are treated with suliobenzoyl dichloride (Annalen, 102, 1857, page 249) or bromoacetyl bromide (Berichte, 24, 1891, page 2219) in the presence of a base to take up the hydrogen halide which is split off, a condensation takes place, and an intermediate compound is formed which has coupling properties and contains a replaceable halogen atom., If this intermediate, which may or may not be isolated, is reacted with another amino compound, again in the presence of a base to take up the hydrogen halide, a second condensation takes place, and a compound is formed which retains its coupling properties and which possesses characteristics introduced by the second amino compound.

In-the case of bromoacetyl bromide, the reaction proceeds as follows:

where R represents a coupler molecule and R represents a second coupler molecule or a heterocyclic system containing an NH- or SH-group.

-: similar reactiontakes-place in the case of sulfobenzoyl dichloride as follows:

NH: O-ooomoomn-Umn Type I. CouplerNH CI-I2 C6 NH-=lieterocyclic.

Type II. Coupler NH CO-+- CsH iH-S2'- NH--heterocyc1ic.

Type III. Heterocyc1ic--NH-CHzCO-NH- coupler.

Type IV. HeterocyclicNHCO-CsH4SOz Couplers containing aminogroups which-may 1 be condensedwith the acyl halide are as follows,

this .list being illustrative only.

NH: HR

CH3- CH5 l I-Ieterocyclic amines containing --NH 1 or #SH o Pyrimil'jine Tetrazole Benzimidazo'le Any of the Eheterocy'clickcompounds disclosd in i Peterson *U.- S: Fatent..2 ,296, 30.6-,--when:-substituted with an -emmofrgroupiimay be employed.

The following examples illustrate the method of forming the compounds according to our invention:

Example -1.---- m( 2 hydroxyphenyhcarbamylv *benzenesulfonyl chloride 'In'" -a'-2"-"liter;* 3--neekdflask;-equipped" with a thermometermndstirrer, placed 5 700' cc. of 'tlioxane "dried over anhydrous calcium chloride. In this solvent is" dissolved l g'fii grams 0.4 mole) "of "recrystallized (from .""parts' of alcohol) o-aminophenol by he'ating'to"70 C. The clear pink solution is cooled to' ""Ci and to it is added 48. grams 10.2 mole). of m-isiil fbhenzoyldichloride with continuousls'tirring. The temperature rises to-about- 40.- and, -after a few minutes, the viscous pinlomaterial. which. has separated,- crystall-izes. After themixture has been stirred for 15 minutesyit iisi-filtered by.suction-andthe residuew of :maminophenolhydrochloride washed- -0n the filter with---1=Q0-:cctofliresh-dioxane.

I The 1 filtrate-adsediluted with 800i T00, :of ligroin enmspmew fon fislminutes. :The sulionyl chloride which sepamtes iis filterecband-Washed on the -filter with l -l'lter f ipetroleum ether. The solid produet is crystallized "'as -f a itan =s'0l i'cl from 600 --'cc. -oftetrachloroethane which has been dried by the distillation-oration? 2500? of forerun. The

mixture-"ls *filtered and the 5 product =washedon the filter with 2X50 "cc. of fresh tetrachloro- "ethanefo'llowwby 300*cci'of hexane to remove "tetrachloroethane. Thei'productis'dried at 100. "Yfe1d 43 g.'(69'% MJP: 186.

'-C-SH+ CHiCOOH NaCl In a 500 cc. 3-necked, flask, equipped with a 2' CH stirrer and a thermometer, is placed 35O cc. of r. 90% acetic acid. To the acid is added. 14.5 g. T E Y ,I T' (0.18 mole) of anhydrous sodium acetate and N N TypeIII 20.0 g. (0.12 mole) of -amino-2-mercaptobenz- 5 I I imidazole. The mixture is heated in a water I I bath to 45. Then is added 37.3 g. 0.12 mole) of 9 in 2'-hydroxyphenylcarbamylbenzenesulfonyl 'chlop y l( e c oy o y p' y -fi'r ide. The mixture is heated in the bath to 55 and ammmiy n held at 55-58 for-2 hours, during vigorous stiri ring. After one-half hour of heating, 2.0 g. (0.012 mole) more of 5-amino-2-mercaptobenzv n N imidazole is added. 5 r CHFC NHCO CH, NH

The cream-colored mixture is cooled to" and V c poured in a thin stream into 1 liter of water. 15 The mixture is filtered by suction, a 6" Biichner N I NH funnel being used.v Theproduct is washed on the 6,

funnel with 3 liters of water. Dried at 50. The

This solid is dissolved by heating in 600 cc. of 1 methanol. The amber methanol solution is i cooled to room temperature and treated with 3.0 i CH 7 grams of Darco. The mixture is filtered by suction through a layer of 3.0 g. otDarco on a CH2 C NH C f Biichner funnel. The clear amber filtrate is 0 N l 'N N Typm concentrated by suctionona steam bath. The f viscous residue pulls and dries to a brittle yellow A A solid, which may be ground. Yield, 34.5 grams H (65 l-phenyl-b l [2' (2" mercapto-4-hydro minions" Example: H a suliamyllbenzamidol-iS-pyrazo one 2-{s'-[3" -(4"'-( tertiary amy1 'shenoxaben'. zene carbamyD-benzene suliamidolvbenzamido}-4-chloro-5-methylphenol (No. 19) "is prepared by the condensation of equimoiecular EHT NHCO SOME weights of Z-(S' a minobenZamid 4-chloror-5- Q I I methylphenol and 3[4 (4"-tertiary amyl phe- If 4 Type II noxy) -benzene carbamyllbenzene sulfonyl chlo- -sn Typ'am Co s" Tide in an excess of quinoline. After the spontaneous reaction excess quinoline f quinonne i0 5-[m-(1u henyl-ls'-pyrazoloite-i-carbagl)ibenzenesulfamidol-z hydrochloride are removed by dilute hydrochlo- 4 I memp 0 mm we ric acid.

E$ mple3 h on l-phenyl-3-{3'-[3"-(4-p-tertiary amyl phe- CHn-0NHSO -CO-NH-C/ c-mn noxy benzene carbamyD-benzene sulfamidol- O L i 1 benzamido}-5-pyrazolone (No. 20) is prepared by the condensation of equimolecular weights of 1- N h phenyl 3 m amino benzoylamino 5 aparaz- $.11, r SH I Type IV olone hydrochloride and 3-[4-(4"-tertiary amyl i v phenoxy)-benzene carbamyll-benzene sulfonyl l-pheny l -iilI?(2"-mercapto4 -hydroxypyrimidyl-o")carbamyll t benzenesuliamidol-Ji-pymzolone I 7. CIHQ O (EH10 ONH A I '.;6L3[3"-(bonzoyl acetylamino)benzene mrbamyH-benzenesuliamido}-2-mercapto benzimidszole chloride in an excess of q'uinolihei Themethodj is similar to'that of Examplel' fi 'f'i Example! I do l-phenyl-3-ani1ino acetylamino-5-pyr amolone (No. 21) is prepared by'heating 1-phenyl-3 b'romoacetylaminoefi-pyrazolone in an excess ofanion N NHCO SO:NH

I p I NH Typell'.

I I 5-[3-(2-hydroxyphenylcarbam 1)-benzene sulfamidoline. Excess aniline is removed by dilute hydro- I a. zmempwbwigmml I 1 chloric acid and during the operati m11 c5 drochloride isalso remo'vedp: I other p unds listed below-are" prepared;

similarly. I I -I I 5-[3- 2-hydroxy4"-methyl-5"-ohlorophenyi carbamynenaene-suliamidol-Z-mwqapto baoziu idalole was 2-mezeapto benzimidazole 5-[m-(2-hydroxy-4-methoxyphenyl-sulfamyl)-benzamido] 2- 'mercapto benzimidazole N 00 CHz-N 20 C-SH CH E/I Type III.

y 2-mercapto benzimidazole 25 wanilinoacetylaminmi-ehloro-i-methylphenol 19. OH I I --NHCO NHSO 2-{ 3-[3-(4-(p-tert. amylphenoxwbeniene'csrb2amylgbeiizeuesulfan idolbenzamido14-ehIoro-5- ma-(z'z-h-ydmlyuhemrl' carbemyl) benzene-N-amylsulfanilide 1s.

' I hen 1-3 nlin cet 1 -5- 1 i1 5[m-(2'-hyd1oxyphen3 ;)l suliauEyD-PenzamidoI-2-mercaptol i, y a 1 yammo pyrazo o e enzimi azo e The aromatic amino developing agents used The following-compound illustrates the union 55 with the coupler compounds of our invention inoi, two coupler molecules containing-H ammo. I V cludewthe'mono diand tri-aminoaryl comgroups by our method: poundsgndztheizde zivatives formed: by substitu- OH tion in the amino group tas WBHfaSlin. the ring,

I such as alkylphenylenediamines and alkyltoluylenediamines. Thesercox npotm'ds are usually used 111. salteiiomr, suchias: the hydrochloride or the sulnhateizi which armmorej stable than t the amines themselYes.:;-= Suitable :cmnpoundseare; vdiethyl-p- 2,2"-dihydroxy-msulfobenzoyldianilide pwphenyienediaminehydrochloride,y diinethyl-phe o ow C po ds illustrate the 00111- Dhenylenediaminehydmohloridewand; dimethylbination of a coupler with a non-coupling arop mphenglenediammeesulphate;;;.Thepammuphenylenediamine hydrochloride, mono-methylmatic amine by our method: phenols and their substitution products may also 1 OH be used where the amino group is unsubstituted. I 'i All of these compounds have an unsubstituted h i ;.SO,NH amino group-which enables the oxidation prodv ueteziof the developer to eouple the colorforming oon pounds to form a dye image;

The following examples are illustrative of dem-(T-IifimkfihhyD-carfirhtl benzene sulieuilide wv opl ssolutionswhichb to develop emulsion layers containing the couplers made according to our invention.

Example 1 p-Aminodiethylaniline sulphate grams 2.5 Sodium sulphite anhydrous do 2 Sodium carbonate anhydrous do 20 Potassium bromide do 1 Water to liters 1 Example 2 p-Aminodiethylaniline hydrochloride grams 2 Sodium sulphite anhydrous do Sodium carbonate anhydrous do Water to liters 1 The couplers used according to my invention may be incorporated in silver halide emulsion layers in various ways but we prefer to form a solution of the sodium salt of the coupler in alcohol and add this to the emulsion. For example, 3 grams of coupler may be dissolved or suspended in 50 cc. of ethyl alcohol and sodium hydroxide added in the amount of 1 equivalent weights of the coupler. The sodium hydroxide may be added as solid or as a concentrate solution. The sodium salt of the coupler is thereby generated in a solution of 50 cc. of alcohol and this solution is added to 1 liter of a gelatin silver halide emulsion.

The pH of the emulsion may then be adjusted if desired by adding a suitable acid such as acetic or sulphuric acid to neutralize all or part of the sodium hydroxide used to form the sodium salt of the coupler.

The coupling components may be incorporated either in gelatin or in other colloidal materials such as collodion, organic esters of cellulose or synthetic resins. The emulsion may be carried by a transparent medium such as glass, cellulose esters, or synthetic resin or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support or superposed layers containing the couplers may be coated on one or both sides of the support. The superposed layers may be differentially sensitized for the formation of a natural color image in the well known manner.

The examples and, compounds set forth in the present specification are illustrative only and it is to be understood that our invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. The method of reacting sulfobenzoyldichloride with two difierent primary amines in successive stages, at least one of which amines contains a group reactive with the oxidation products of primary aromatic amino photographic developing agents, which comprises selectively reacting a cool solution of one of said amines with the carboxylic acid chloride group of said sulfobenzcyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulfonic acid amide.

2. The method of reacting sulfobenzoyldichloride with two different primary amines in successive stages, one of which amines contains a reactive methylene roup and the other of which amines contains a 5-membered heterocyclic group containing a mercapto group, which comprises selectively reacting a cool solution of one of said amines with the carboxylic acid chloride group of said suliobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulfonic acid amide.

3. The method of reacting sulfobenzoyldichloride in successive stages, with a l-phenyl pyrazolone having a reactive methylene group in the 4-position and having a primary amino substituent, and with 5-amino-2-mercaptobenzimidazole, which comprises selectively reacting a cool solution of one or said amines with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulionic acid amide.

4. The method of reacting sulfobenzoyldichloride in successive stages, with a l-phenyl pyrazolone having a reactive methylene group in the 4-position and having a primary amino substitu- 1 cut, and with 5-amino-2-mercaptobenzimidazole, which comprises selectively reacting a cool solution of said pyrazolone with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group,

and then heating said reaction product with said S-amino-2-mercaptobenzimidazole to produce a sulfonic acid amide.

5. The method of reacting sulfobenzoyldichloride in successive stages, with a phenol having a primary amino group in the 2-position, and with 5-amino-2-mercaptobenzimidazole, which comprises selectively reacting a cool solution of one of said amines with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulfonic acid amide.

6. The method of reacting sulfobenzoyldichloride in successive stages, with a phenol having a primary amino group in the 2-position, and with 5-amino-2-mercaptobenzimidazole, which comprises selectively reacting a cool solution of said phenol with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with said 5-amino- Z-mercaptobenzimidazole to produce a sulfonic acid amide.

ARNOLD WEISSBERGER. ILMARI F. SALMINEN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name I Date 1,663,474 Ackerman Mar. 20, 1928 FOREIGN PATENTS Number Country Date 503,752 Great Britain 1939 

